CN112694927B - Anti-rust oil composition and preparation method thereof - Google Patents

Anti-rust oil composition and preparation method thereof Download PDF

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CN112694927B
CN112694927B CN201911009014.9A CN201911009014A CN112694927B CN 112694927 B CN112694927 B CN 112694927B CN 201911009014 A CN201911009014 A CN 201911009014A CN 112694927 B CN112694927 B CN 112694927B
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linear
independently selected
branched alkyl
general formula
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CN112694927A (en
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胡海豹
陈晓伟
史军
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/12—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having a phosphorus-to-carbon bond
    • C10M137/14—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having a phosphorus-to-carbon bond containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having sulfur atoms, with or without selenium or tellurium atoms, as the only ring hetero atoms
    • C07F9/655309—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having sulfur atoms, with or without selenium or tellurium atoms, as the only ring hetero atoms the sulfur atom being part of a three-membered ring
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C10M169/044—Mixtures of base-materials and additives the additives being a mixture of non-macromolecular and macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/121—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
    • C10M2207/123—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms polycarboxylic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/283—Esters of polyhydroxy compounds
    • C10M2207/2835—Esters of polyhydroxy compounds used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
    • C10M2215/065—Phenyl-Naphthyl amines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/041—Triaryl phosphates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/06—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon bonds
    • C10M2223/065—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon bonds containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
    • C10M2229/04—Siloxanes with specific structure
    • C10M2229/041—Siloxanes with specific structure containing aliphatic substituents

Abstract

The invention provides an anti-rust oil composition and a preparation method thereof. The anti-rust oil composition comprises the following components: A) the thiophosphonate compound accounts for 0.1 to 10 percent of the total mass of the composition; B) antioxidant accounting for 0.1-10% of the total weight of the composition; C) the antirust agent accounts for 1-15% of the total mass of the composition; D) optional antifoaming agent, accounting for 0-200 ppm of the total weight of the composition; E) a major amount of a lubricating base oil; wherein the structure of the thiophosphonate compound is shown as the general formula (I):

Description

Anti-rust oil composition and preparation method thereof
Technical Field
The invention relates to an anti-rust oil composition, in particular to an anti-rust oil composition with excellent extreme pressure anti-wear performance.
Background
The anti-rust oil is a special lubricant and is generally applied to special working occasions. Because the service environment is harsh, the extreme pressure antiwear performance of the lubricant is often required to be special. For this reason, it is generally necessary to select an extreme pressure antiwear agent having excellent properties.
The extreme pressure antiwear agents widely used in the field of lubricating oil at present include tricresyl phosphate (T306), ammonium thiophosphate (T307), thiophosphate (IRGALUBE 353), ammonium phosphate (IRGALUBE 349), and the like, but their antiwear and antifriction properties need to be further improved. There are also many patents relating to extreme pressure anti-wear agents, for example, CN 1396169a discloses a thiophosphate ester type extreme pressure anti-wear agent, which can effectively improve the anti-wear and anti-wear properties of a lubricant using liquid paraffin as base oil. CN 106317109A discloses a thiophosphate type extreme pressure antiwear agent, which is used as a hydraulic oil or lubricating oil additive and shows better antirust performance, thermal stability, filterability and hydrolytic stability, but the antiwear and antifriction properties of the thiophosphate type extreme pressure antiwear agent are not outstanding. CN 101724492A discloses a zinc dithiophosphate extreme pressure antiwear agent, which is an organic metal salt and does not conform to the development trend of ashing of lubricating oil additives.
Disclosure of Invention
The invention provides an anti-rust oil composition and a preparation method thereof.
The anti-rust oil composition comprises the following components:
A) a thiophosphonate compound, which accounts for 0.1-10% (preferably 1-5%) of the total mass of the composition;
B) antioxidant accounting for 0.1-10% (preferably 0.5-5%) of the total mass of the composition;
C) the antirust agent accounts for 1-15% (preferably 2-10%) of the total mass of the composition;
D) optional antifoaming agent, 0 to 200ppm (preferably 1 to 50ppm) of the total weight of the composition;
E) a major amount of a lubricating base oil;
wherein the structure of the thiophosphonate compound is shown as the general formula (I):
Figure BDA0002243627240000021
in the general formula (I), the radical R0Selected from H, C6～C20Aryl radical, C1-300Straight or branched chain alkyl (preferably phenyl, C)1～C14Alkyl phenyl, C1～C20Straight or branched chain alkyl); each radical R1、R2、R3、R4、R5Are the same or different from each other and are each independently selected from H, C1～C20A linear or branched alkyl group and a group of the formula (II), each group R1、R2、R3、R4、R5At least one group of (a) is a group represented by formula (II);
Figure BDA0002243627240000022
in the general formula (II), the group R1' is selected from the group consisting of a single bond, C1-20Straight or branched alkylene (preferably selected from the group consisting of single bond and C)1-4Straight or branched chain alkylene); radicals R in n repeating units2' equal to or different from each other, each independently selected from the group consisting of 2-, 3-and 4-valent C1-20Straight or branched chain alkyl (preferably each independently selected from 2-, 3-or 4-valent C1-4Straight or branched chain alkyl); radicals R in n repeating units3' the same or different from each other, each independently selected from the group consisting of a single bond, and C having a valence of 2 or 31-20Straight or branched chain alkyl (preferably each independently selected from single bond, 2-valent or 3-valent C1-4Straight or branched chain alkyl); radicals R in n repeating units4' the same or different from each other, each independently selected from a single bond, C having a valence of 2 or 31-20Straight or branched chain alkyl (preferably each independently selected from single bond, 2-valent or 3-valent C1-4Straight or branched chain alkyl); radicals R in n repeating units5' equal to or different from each other, each independently selected from the group consisting of 2-, 3-and 4-valent C1-20Straight or branched chain alkyl (preferably each independently selected from 2-, 3-or 4-valent C1-4Straight or branched chain alkyl); radicals R in n repeating units6' the same or different from each other, each independently selected from the group consisting of a single bond, C1-20Straight or branched alkylene (preferably each independently selected from single bond, C)1-4Linear or branched alkylene); radical R7' is selected from hydrogen, C1-20Straight or branched alkyl (preferably selected from hydrogen, C)1-4Straight or branched chain alkyl); n is an integer of 1 to 10 (preferably an integer of 1 to 3); m in the n repeating units are the same or different from each other and are each independently selected from integers of 0 to 10 (preferably integers of 0 to 5); m' in the n repeating units are the same or different from each other, and are each independently selected from integers of 0 to 10 (preferably integers of 0 to 5); in each repeating unit of formula (II), when m is greater than 0, m S atoms are bound to the radical R2'、R5' bonding; when m 'is greater than 0, m' S atoms and the radical R3'、R4' bonding; in each repeating unit of formula (II), when the radical R3When 'is a single bond, m' S atoms and the group R2' bonding when the group R4'when it is a single bond, m' S atoms and the group R5' bonding.
According to the invention, in the general formula (I), preferably the radicals R1、R3、R5Are the same or different from each other and are each independently selected from hydrogen and C1-4A linear or branched alkyl group; each radical R2、R4Are the same or different from each other and are each independently selected from hydrogen and C1-300Straight or branched chain hydrocarbon radical (preferably C)1-30A linear or branched alkyl group or a polyolefin group having a number average molecular weight Mn of 300-3000), a group represented by the general formula (II), wherein at least one group is selected from the group represented by the general formula (II). Further preferably, in at least one group represented by the general formula (II), at least one of m and m' is greater than 0.
According to the invention, in the general formula (I), it is further preferred for each radical R1、R3、R5Are the same or different from each other and are each independently selected from hydrogen and C1-4A linear or branched alkyl group; each radical R2、R4One group is selected from the group represented by the general formula (II) and the other group is selected from hydrogen. Further preferably, in at least one group of formula (II), at least one of m and m' is greater than 0.
According to the invention, the thiophosphonate compound may be selected from the following specific compounds or mixtures thereof in any proportion.
Figure BDA0002243627240000031
Figure BDA0002243627240000041
According to the present invention, the method for producing a thiophosphonate compound comprises a step of subjecting a phenol compound represented by the general formula (X) to a sulfurization reaction, a phosphonothioylation reaction;
Figure BDA0002243627240000042
in the general formula (X), the radicals R1”、R2”、R3”、R4”、R5"equal to or different from each other, each independently selected from hydrogen, C1-300Straight or branched chain hydrocarbon radical (preferably C)1-30A linear or branched alkyl group or a polyolefin group having a number average molecular weight Mn of 300-3000), a group represented by the formula (Y), wherein at least one group is selected from the group represented by the formula (Y);
Figure BDA0002243627240000043
wherein the radical R1"' is selected from a single bond, C1-20Straight or branched alkylene (preferably selected from the group consisting of single bond and C)1-4Straight or branched chain alkylene); radicals R in m repeating units2"' same or different from each other, each independently selected from the group consisting of a single bond, C1-20Straight or branched alkylene (preferably each independently selected from the group consisting of a single bond, C1-4Linear or branched alkylene); radical R3"' is selected from hydrogen, C1-20Straight or branched alkyl (preferably selected from hydrogen, C)1-4Straight or branched chain alkyl); radical R in m repeating units4"' equal to or different from each other, each independently selected from hydrogen, C1-20Straight or branched chain alkyl (preferably each independently selected from hydrogen, C1-4Straight or branched chain alkyl); radicals R in m repeating units5"' equal to or different from each other, each independently selected from hydrogen, C1-20Straight or branched chain alkyl (preferably each independently selected from hydrogen, C1-4Straight or branched chain alkyl); m is a positive integer (preferably a positive integer between 1 and 10, more preferably a positive integer between 1 and 3).
According to the invention, in the general formula (X), preferably the radicals R1”、R3”、R5"equal to or different from each other, each independently selected from hydrogen, C1-4A linear or branched alkyl group; each radical R2”、R4"equal to or different from each other, each independently selected from hydrogen, C1-20A linear or branched alkyl group and a group represented by the general formula (Y), wherein at least one group is selected from the group represented by the general formula (Y).
According to the invention, in the general formula (X), it is further preferred that each radical R1”、R3”、R5"equal to or different from each other, each independently selected from hydrogen, C1-4A linear or branched alkyl group; each radical R2”、R4One group in "is selected from the group represented by the general formula (Y), and the other group is selected from hydrogen.
According to the present invention, the phenol compound represented by the general formula (X) may be first subjected to a sulfurization reaction and then subjected to a sulfurization reaction to produce a sulfurized product (sulfurized product of the phenol compound represented by the general formula (X)), or the phenol compound represented by the general formula (X) may be first subjected to a sulfurization reaction and then subjected to a sulfurization reaction to produce a sulfurized product (sulfurized product of the phenol compound represented by the general formula (X)).
According to the present invention, the sulfurization reaction includes a step of reacting the phenol compound represented by the general formula (X) or the phosphonothioylation product of the phenol compound represented by the general formula (X) with a sulfurizing agent. The sulfurization reaction causes the sulfurization agent to have electrophilic addition reaction with carbon-carbon double bond (olefinic bond), and when the molecule has 1 carbon-carbon double bond, monosulfuride can be generated, and when the molecule has a plurality of carbon-carbon double bonds, monosulfuride and polysullfuride can be generated. The vulcanizing agent is preferably inorganic vulcanizing agent and/or organic vulcanizing agent, and the inorganic vulcanizing agent can be selected from sulfur and Na2S、K2S、ZnS、H2One or more of S and SCl; the organic vulcanizing agent can be one or more of di-tert-butyl sulfide (DBPS), dimethyl disulfide (DMDS), dimethyl sulfide (DMS), Ethyl Mercaptan (EM), n-butyl mercaptan (NBM) and tert-nonyl polysulfide (TNPS); the vulcanizing agent is more preferably sulfur and Na2S and thiol. In the sulfurization reaction, phenol represented by the general formula (X) is combinedMolar ratio of compound to vulcanizing agent 1: 1 to 6, more preferably 1: 2 to 4. The temperature of the vulcanization reaction is 100-240 ℃, preferably 140-190 ℃; generally speaking, the longer the reaction time, the higher the conversion, and the reaction time is generally 0.5 to 10 hours, preferably 3 to 5 hours, in combination with the conversion of the reaction and the economy of the reaction.
According to the invention, the catalyst may or may not be added, preferably. The catalyst is preferably selected from C1～6The organic amine and inorganic base of (b) may be selected from, for example, one or more of methylamine, dimethylamine, ethylamine, diethylamine, propylamine, dipropylamine, tripropylamine, butylamine, pentylamine, hexylamine, aqueous ammonia, sodium hydroxide, potassium hydroxide, zinc hydroxide, sodium oxide, potassium oxide, zinc oxide, sodium carbonate, potassium carbonate and zinc carbonate. The mass of the catalyst is 0.01 to 10%, preferably 0.1 to 5% of the mass of the phenol compound represented by the general formula (X).
According to the present invention, after the completion of the sulfurization reaction, the reaction product may be subjected to a purification treatment by one or more methods selected from the group consisting of water washing, distillation, filtration, drying and recrystallization, without any particular limitation; when the organic amine and/or inorganic base catalyst is added in the vulcanization reaction, the purification treatment method comprises one or more of acid washing, water washing, distillation, filtration, drying and recrystallization.
According to the invention, preferably, the structure of the sulfur-phosphorus acylating agent is shown as the formula (Z):
Figure BDA0002243627240000061
wherein R is0Selected from H, C6～C20Aryl radical, C1-300Straight or branched chain alkyl (preferably phenyl, C)1～C14Alkyl phenyl, C1～C20Straight or branched chain alkyl); the group A is selected from F, Cl, Br, I, OH (preferably Cl, Br). Specifically, the thiophosphoryl chloride, thiophosphonyl dichloride and C can be selected as the thiophosphoryl acylating agent1-300Straight chainOr one or more of branched alkyl thiophosphonyl dichloride and phenyl thiophosphonyl dichloride (preferably phenyl thiophosphonyl dichloride).
According to the present invention, it is preferred that the reaction conditions of the sulfurized product of the phenol compound represented by the general formula (X) or the phenol compound represented by the general formula (X) with a thiophosphoryl acylating agent are: the mol ratio of the sulfur-phosphorus acylating agent to the phenol compound shown in the general formula (X) is 1: 1 to 10 (preferably 1: 1 to 5); the reaction temperature is 50-150 ℃ (preferably 60-100 ℃); in general, the conversion is higher as the reaction time is longer, and the reaction time is usually 0.5 to 10 hours (preferably 3 to 5 hours). In the phosphono-acylation reaction, a catalyst may or may not be added, and preferably is added. The catalyst is preferably C1～10The organic amine and inorganic ammonium of (b) may be selected from, for example, one or more of methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, butylamine, dibutylamine and ammonia. The amount of the catalyst added is preferably 0.1 to 60%, more preferably 10 to 40% by mass of the phenol compound. In the phosphonothioacylation reaction, a solvent may be added or may not be added, and the solvent is preferably added. The solvent is preferably one or more of toluene, xylene, petroleum ether and cyclohexane, and for example, toluene and/or xylene may be used. The amount of the solvent to be used is 50 to 500% (preferably 100 to 300%) by mass of the phenol compound represented by the general formula (X). The catalyst and the solvent may be removed by one or more methods including acid washing, water washing, distillation, filtration, drying and recrystallization, and are not particularly limited.
According to the present invention, after the completion of the reaction of the sulfurized product of a phenol compound represented by the above general formula (X) or the reaction of the phenol compound represented by the above general formula (X) with a thiophosphoryl acylating agent, the reaction product may be subjected to a purification treatment by one or more methods selected from among washing with water, distillation, filtration, drying and recrystallization, without particular limitation.
According to the present invention, the phenol compound represented by the general formula (X) is preferably derived from a natural plant cashew nut. The cashew nut shells contain a large amount of cashew nut shell oil, the main component of the cashew nut shell oil is meta-phenol, generally called cardanol, and the structure of the cashew nut shell oil is as follows:
Figure BDA0002243627240000071
wherein R is C15H(31+x)And x is 0, -2, -4 or-6.
The thiophosphonate compounds of the present invention may be compounds of a single structure or may be mixtures comprising compounds of different structures.
The thiophosphonate compound has outstanding bearing capacity and excellent wear resistance and wear reduction performance, can be used as an extreme pressure anti-wear agent to be applied to lubricating oil and lubricating grease, and has the advantages of simple preparation method, convenient operation, green and easily obtained raw materials, high product yield and high purity.
According to the invention, the antioxidant can be amine antioxidant and/or phenol antioxidant, for example, one or more of N-phenyl-naphthylamine, octyl diphenylamine, butyl diphenylamine, phenothiazine, 2, 6-di-tert-butyl-p-cresol and 2, 6-di-tert-butyl-cresol can be selected, amine antioxidant is preferred, and commonly used trade marks include T531, V81, T511 and T501.
According to the invention, the rust inhibitor can be one or more of phosphate amine salt, alkenyl succinate, alkaline barium naphthalene sulfonate and barium petroleum sulfonate, preferably phosphate amine salt and/or alkenyl succinate, and commonly used commercial brands comprise T703, T746, T747 and T701.
According to the invention, the optional antifoam agent may be chosen from methylsilicones and/or siloxanes, preferably methylsilicones, commonly used trade designations including T901.
According to the invention, the lubricating base oil is preferably a synthetic lubricating base oil, for example an ester synthetic base oil and/or a polyalphaolefin synthetic oil may be selected. The ester synthetic base oil is preferably a polyol ester base oil and/or a diester base oil, and more preferably a polyol ester base oil. The polyol ester base oil may be one or more selected from trimethylolpropane ester and pentaerythritol ester, for example, trimethylolpropane oleate, trimethylolpropane stearate, pentaerythritol oleate and pentaerythritol stearate. The diester can be one or more of dioctyl sebacate, dioctyl adipate, dioctyl methyladipate, hexanediol dicaprylate and decanediol dicaprylate.
The method for producing the rust preventive oil composition of the present invention comprises a step of mixing the above-mentioned respective components. The mixing temperature is preferably between 40 ℃ and 90 ℃ and the mixing time is preferably between 1 hour and 6 hours.
The anti-rust oil composition disclosed by the invention has excellent anti-rust performance, degradation performance and extreme pressure anti-wear performance, and is high in bearing capacity and good in compatibility.
Detailed Description
Unless otherwise specified, the percentages mentioned below are percentages by mass.
The present invention will be further illustrated by the following examples and comparative examples, but the present invention is not limited thereto.
According to the invention, as said C1-300Straight or branched alkyl, such as C1-20Straight or branched chain alkyl (preferably C)1-10Straight or branched alkyl, more preferably C1-4Linear or branched alkyl) or polyolefin based. Specific examples of the polyolefin group include a polyolefin group having a number average molecular weight Mn of 300-3000. In this case, the number average molecular weight Mn of the polyolefin group is preferably 500-2000, more preferably 500-1500. According to the present invention, the polyolefin group is (substantially) saturated (exhibits a long chain alkyl structure), but depending on the kind of the polyolefin as a starting material or the method of producing the polyolefin, the polyolefin group may also contain a small amount of olefinic double bonds in the molecular chain (such as those remaining or introduced during the production of the polyolefin), but this does not affect the achievement of the effect of the present invention, and the present invention does not intend to specify the amount, and the present invention still classifies such polyolefin group as an "alkyl group".
In the present specification, the term "single bond" is sometimes used in the definition of a group. By "single bond" is meant that the group is absent. For example, falseHas a structure of-CH2-A-CH3Wherein the group a is defined as being selected from the group consisting of single bonds and methyl groups. In this connection, if A is a single bond, this means that the group A is absent, in which case the formula is correspondingly simplified to-CH2-CH3。
In the context of the present specification, the expression "number + valence + group" or the like refers to a group obtained by removing the number of hydrogen atoms represented by the number from the basic structure (such as a chain, a ring, a combination thereof, or the like) to which the group corresponds, and preferably refers to a group obtained by removing the number of hydrogen atoms represented by the number from a carbon atom (preferably a saturated carbon atom and/or a non-identical carbon atom) contained in the structure. For example, "3-valent straight-chain or branched alkyl" refers to a group obtained by removing 3 hydrogen atoms from a straight-chain or branched alkane (i.e., the base chain to which the straight-chain or branched alkyl corresponds), and "2-valent straight-chain or branched heteroalkyl" refers to a group obtained by removing 2 hydrogen atoms from a straight-chain or branched heteroalkane (preferably from a carbon atom contained in the heteroalkane, or further, from a non-identical carbon atom). For example, the 2-valent propyl group can be-CH2-CH2-CH2－*、
Figure BDA0002243627240000091
The 3-valent propyl group may be
Figure BDA0002243627240000092
The 4-valent propyl group may be
Figure BDA0002243627240000093
Wherein x represents a binding end in the group that may be bonded to other groups.
According to the invention, in each recurring unit of formula (II), when m is greater than 0, m S atoms are bonded to the radical R2'、R5' bonding; when m 'is greater than 0, m' S atoms and the radical R3'、R4' bonding; in each repeating unit of formula (II), when the radical R3When 'is a single bond, m' S atoms and the group R2' bonding when the group R4When is a single bond, m' S atom and group R5' bonding.
According to the invention, in each recurring unit of formula (II), when m is 0, there is no S atom with the radical R2'、R5' bonding; when m' is 0, there is no S atom with the group R3'、R4' bonding; in each repeating unit of formula (II), when the radical R3'when not a single bond, m' S atoms and the group R3' bonding when the group R4'if not singly bound, m' S atoms with radicals R4' bonding.
According to the invention, in each recurring unit of the formula (II), the radical (S)m、(S)m’、R2'、R3'、R4'、R5' bond formation rules are met.
According to the invention, m S atoms are bound to the radical R2'、R5' bonding means that the terminal S atom of the m S atoms (or only one S atom present) is bonded to the group R2'、R5' bonded (when m is 1, there is only one S atom, when this S atom is bonded to the group R2'、R5A 'bond'); m' S atoms and radicals R3'、R4'bonding means that the terminal S atom of the m' S atoms (or only one S atom present) is bonded to the group R3'、R4'bonded (when m' is 1, there is only one S atom, in which case this S atom is bound to the radical R3'、R4A 'bond').
According to the invention, in each recurring unit of formula (II), in the radical R2'、R3'、R4'、R5' when bonded to each other, may be bonded via the group R2'、R3'、R4'、R5Either of the binding termini of' form a covalent bond. In each repeating unit of formula (II), in the group (S)mOr (S)m' and R2'、R3'、R4'、R5' when bonded to each other, may be bonded to the group R2'、R3'、R4'、R5Either of the binding termini of' form a covalent bond.
According to the invention, in each recurring unit of the formula (II), when the radical R is3'、R4' non-single bond, m ' is greater than 0, m ' S atoms and the group R3'、R4' bonding, R3'、R4' Each is independently selected from the group consisting of 3 valent C1-20Straight or branched chain alkyl (preferably each independently selected from 3 valent C1-4Straight or branched chain alkyl); when the group R3'、R4'non-single bond, when m' is 0, there is no S atom and no group R3'、R4' bonding, R3'、R4' Each is independently selected from 2-valent C1-20Straight or branched chain alkyl (preferably each independently selected from 2 valent C1-4Straight or branched chain alkyl).
According to the invention, in each recurring unit of the formula (II), when the radical R3'、R4' non-single bond, when m is greater than 0, R2'、R5' Each is independently selected from the group consisting of 3 valent C1-20Straight or branched chain alkyl (preferably each independently selected from 3 valent C1-4Straight or branched chain alkyl); when the group R3'、R4' non-single bond, when m is 0, R2'、R5' Each is independently selected from 2-valent C1-20Straight or branched chain alkyl (preferably each independently selected from 2 valent C1-4Straight or branched chain alkyl).
According to the invention, in each recurring unit of the formula (II), when the radical R is3' is a single bond, R4' non-single bond, when m ' is greater than 0, m ' S atoms and the group R2'、R4' bonding, R4' selected from 3-valent C1-20Straight or branched chain alkyl (preferably each independently selected from 3 valent C1-4Straight or branched chain alkyl); when the group R3' is a single bond, R4'non-single bond, when m' is 0, there is no S atom and no group R2'、R4' bonding, R4' selected from 2-valent C1-20Straight or branched chain alkyl (preferably each independently selected from 2 valent C1-4Straight or branched chain alkyl).
According to the invention, in each recurring unit of the formula (II), when the radical R is3' is a single bond, R4' non-single bond, when m is greater than 0, R2' selected from the group consisting of C having a valence of 41-20Straight or branched alkyl (preferably selected from C having a valence of 4)1-4Straight or branched chainAlkanyl) R5' selected from 3-valent C1-20Straight or branched alkyl (preferably selected from 3-valent C)1-4Straight or branched chain alkyl); when the group R3' is a single bond, R4' non-single bond, when m is 0, R2' selected from 3-valent C1-20Straight or branched chain alkyl (preferably selected from 3-valent C1-4Straight or branched alkyl), R5' selected from 2-valent C1-20Straight or branched chain alkyl (preferably selected from 2-valent C1-4Straight or branched chain alkyl).
According to the invention, in each recurring unit of the formula (II), when the radical R3' non-Single bond, R4' is a single bond, m ' is greater than 0, m ' S atoms are bonded to the group R3'、R5' bonding, R3' selected from 3-valent C1-20Straight or branched chain alkyl (preferably each independently selected from 3 valent C1-4Straight or branched chain alkyl); when the group R3' non-Single bond, R4When 'is a single bond and m' is 0, there is no S atom or group R3'、R5' bonding, R3' selected from the group consisting of 2-valent C1-20Straight or branched chain alkyl (preferably each independently selected from 2 valent C1-4Straight or branched chain alkyl).
According to the invention, in each recurring unit of the formula (II), when the radical R3' non-Single bond, R4' is a single bond, when m is greater than 0, R2' selected from the group consisting of 3-valent C1-20Straight or branched alkyl (preferably selected from 3-valent C)1-4Straight or branched alkyl), R5' selected from the group consisting of C having a valence of 41-20Straight or branched chain alkyl (preferably selected from C having a valence of 4)1-4Straight or branched chain alkyl); when the group R3' non-Single bond, R4' is a single bond, when m is 0, R2' selected from the group consisting of 2-valent C1-20Straight or branched alkyl (preferably selected from 2-valent C)1-4Straight or branched alkyl), R5' selected from 3-valent C1-20Straight or branched chain alkyl (preferably selected from 3-valent C1-4Straight or branched chain alkyl).
According to the invention, in each recurring unit of the formula (II), when the radical R3'、R4' are all single bonds, m ' is greater than 0, m ' S atoms and the group R2'、R5' KeyWhen m is greater than 0, R2'、R5' Each is independently selected from 4-valent C1-20Straight or branched chain alkyl (preferably each independently selected from C having a valence of 41-4Straight or branched chain alkyl), when m is 0, R2'、R5' Each is independently selected from the group consisting of 3 valent C1-20Straight or branched chain alkyl (preferably each independently selected from 3 valent C1-4Straight or branched chain alkyl).
According to the invention, in each recurring unit of the formula (II), when the radical R3'、R4When 'are all single bonds, m' is 0, and m is greater than 0, R2'、R5' Each is independently selected from 3-valent C1-20Straight or branched chain alkyl (preferably each independently selected from 3 valent C1-4Straight or branched chain alkyl); when the group R3'、R4When 'are all single bonds, m' is 0, and m is 0, R2'、R5' Each is independently selected from 2-valent C1-20Straight or branched chain alkyl (preferably each independently selected from 2 valent C1-4Straight or branched chain alkyl).
According to the present invention, in each repeating unit of formula (II), for example, a structure may be formed including: -CH2-CH2-CH2-CH2-CH2-*、
Figure BDA0002243627240000111
Figure BDA0002243627240000112
The main raw materials used are as follows:
cashew nut shell oil, Shanghai Bingshi chemical Co Ltd, Industrial products
Sulfur powder, national chemical reagent group, Inc., analytical purity
Triethylamine, chemical reagent of national drug group, analytical purity
Phenylthiophosphonodichloride, national pharmaceutical group chemical reagents Ltd, analytical purity
Trimethylphenol phosphate, TCP, Nengmadzu chemical Co., Ltd, Industrial products
Octyl diphenylamine, V81, Beijing rifampicin commercial Co., Ltd, industrial products
N-phenyl-naphthylamine, T531, Tianjin Yuning chemical Co., Ltd, Industrial products
Alkenyl succinate, T703, N.C. Hi-Tech Co., Ltd, Beijing Huarui, Industrial products
Basic barium naphthalenesulfonate, T747, N.C. Beijing Huarui Newcastle science and technology Co., Ltd
Methyl Silicone oil, T901, Beijing Huarui New City science and technology Co., Ltd, Industrial products
Polyol ester base oil, Hi-Tech Co Ltd of Beijing Huarui New City, Industrial products
Example 1 preparation of sulfurized cardanol
62g of cardanol (ca. 0.2mol) and 12.8g of sulfur powder (0.4mol) were placed in a 250ml three-neck reaction flask, and stirring and heating were started. The reaction temperature was maintained at 190 ℃ and the reaction was continued for 3 hours. And after the reaction is finished, cooling, and filtering to obtain dark brown red viscous liquid, namely the vulcanized cardanol, wherein the product conversion rate is 89.3%.
Example 2 preparation of Cardanol phenyl thiophosphonate disulphide
25g of sulfurized cardanol prepared in example 1, 8g of triethylamine and 50g of toluene were placed in a reaction flask, and heated with stirring, 5g of phenylthiophosphonyl dichloride was added thereto, and the reaction temperature was maintained at 90 ℃ for 4 hours. And cooling after the reaction is finished to obtain a brownish red transparent liquid. Washing the reaction product with distilled water to neutrality, distilling the organic phase at 100Pa and 150 deg.c under reduced pressure for 1 hr to eliminate water and solvent to obtain brown yellow transparent liquid with reaction conversion rate of 95.1%.
Examples 3 to 6 of Rust preventive oil composition and comparative example 1
The formulation compositions of examples 3 to 6 of the rust preventive oil composition and comparative example 1 are shown in Table 1. Adding the components into a mixing container in proportion, heating and stirring for 4 hours at 80 ℃, and respectively preparing the anti-rust oil composition.
TABLE 1
Figure BDA0002243627240000121
The examples and comparative examples of the rust preventive oil composition were subjected to the examination of frictional properties, the examination of indexes such as flash point, acid value before and after oxidation, wet box, pour point, evaporation loss, etc., and the test results are shown in Table 2.
TABLE 2
Figure BDA0002243627240000131

Claims (20)

1. An anti-rust oil composition comprising the following components:
A) the thiophosphonate compound accounts for 0.1 to 10 percent of the total mass of the composition;
B) antioxidant, accounting for 0.1% -10% of the total weight of the composition;
C) the antirust agent accounts for 1-15% of the total mass of the composition;
D) optional antifoaming agent, accounting for 0-200 ppm of the total weight of the composition;
E) a major amount of a lubricating base oil;
wherein the structure of the thiophosphonate compound is shown as the general formula (I):
Figure FDA0003613543160000011
in the general formula (I), the radical R0Selected from H, C6～C20Aryl radical, C1-300A linear or branched alkyl group; each radical R1、R2、R3、R4、R5Are the same or different from each other and are each independently selected from H, C1～C20A linear or branched alkyl group and a group of the formula (II), each group R1、R2、R3、R4、R5At least one group of (a) is a group represented by the formula (II);
Figure FDA0003613543160000012
in the general formula (II), the group R1' is selected from a single bond, C1-20A linear or branched alkylene group; radicals R in n repeating units2' the same or different from each other, each independently selected from the group consisting of 2-, 3-or 4-valent C1-20A linear or branched alkyl group; radicals R in n repeating units3' the same or different from each other, each independently selected from a single bond, C having a valence of 2 or 31-20A linear or branched alkyl group; radicals R in n repeating units4' the same or different from each other, each independently selected from the group consisting of a single bond, and C having a valence of 2 or 31-20A linear or branched alkyl group; radicals R in n repeating units5' the same or different from each other, each independently selected from the group consisting of 2-, 3-or 4-valent C1-20A linear or branched alkyl group; radicals R in n repeating units6' the same or different from each other, each independently selected from the group consisting of a single bond, C1-20A linear or branched alkylene group; radical R7' is selected from hydrogen, C1-20A linear or branched alkyl group; n is an integer of 1 to 10; m in the n repeating units are the same or different and are respectively and independently selected from integers between 0 and 10; m' in the n repeating units are the same or different and are independently selected from integers between 0 and 10; in each repeating unit of formula (II), when m is greater than 0, m S atoms are bound to the radical R2'、R5' bonding; when m 'is greater than 0, m' S atoms are bound to the radical R3'、R4' bonding; in each repeating unit of formula (II), when the radical R3When 'is a single bond, m' S atoms and the group R2' bonding when the group R4When 'is a single bond, m' S atoms and the group R5' bonding; in at least one group of the formula (II), at least one of m and m' is greater than 0.
2. The composition of claim 1, wherein the thiophosphonate compound comprises 1% to 5% of the total weight of the composition; the antioxidant accounts for 0.5 to 5 percent of the total mass of the composition; the antirust agent accounts for the total mass of the composition2% -10%; the optional antifoaming agent accounts for 1-50 ppm of the total mass of the composition; in the general formula (I), the radical R0Selected from phenyl, C1～C14Alkyl phenyl, C1～C20A linear or branched alkyl group; in the general formula (II), the group R1' is selected from the group consisting of a single bond and C1-4A linear or branched alkylene group; radicals R in n repeating units2' Each is independently selected from 2, 3 or 4 valent C1-4A linear or branched alkyl group; radicals R in n repeating units3' each is independently selected from a single bond, 2-valent or 3-valent C1-4A linear or branched alkyl group; radicals R in n repeating units4' each is independently selected from a single bond, 2-valent or 3-valent C1-4A linear or branched alkyl group; radicals R in n repeating units5' Each is independently selected from 2, 3 or 4 valent C1-4A linear or branched alkyl group; radicals R in n repeating units6' each is independently selected from the group consisting of a single bond, C1-4A linear or branched alkylene group; radical R7' is selected from hydrogen, C1-4A linear or branched alkyl group; n is an integer of 1 to 3; m in the n repeating units is independently selected from an integer between 0 and 5; m' in the n repeating units is independently selected from integers of 0-5.
3. Composition according to claim 1, characterized in that, in the formula (I), the radicals R1、R3、R5Are the same or different from each other and are each independently selected from hydrogen, C1-4A linear or branched alkyl group; each radical R2、R4Are the same or different from each other and are each independently selected from hydrogen, a group represented by the general formula (II), wherein at least one group is selected from a group represented by the general formula (II).
4. Composition according to claim 1, characterized in that, in the formula (I), the radicals R1、R3、R5Are the same or different from each other and are each independently selected from hydrogen, C1-4A linear or branched alkyl group; each radical R2、R4One group in (B) is selected from the group represented by the general formula (II)And the other group is selected from hydrogen.
5. A composition according to claim 1, wherein the thiophosphonate compound is selected from the group consisting of:
Figure FDA0003613543160000031
Figure FDA0003613543160000041
6. the composition according to claim 1, wherein the thiophosphonate compound is prepared by a method comprising the steps of subjecting the phenol compound represented by the general formula (X) to a sulfurization reaction, a phosphonothioylation reaction;
Figure FDA0003613543160000042
in the general formula (X), the radicals R1”、R3”、R5"equal to or different from each other, each independently selected from hydrogen, C1-4A linear or branched alkyl group; each radical R2”、R4"equal to or different from each other, each independently selected from hydrogen, C1-20A linear or branched alkyl group and a group represented by the general formula (Y), wherein at least one group is selected from the group represented by the general formula (Y);
Figure FDA0003613543160000043
wherein the radical R1'' is selected from the group consisting of a single bond, C1-20A linear or branched alkylene group; radicals R in m repeating units2'' are the same or different from each other and are each independently selected from the group consisting of a single bond, C1-20Straight or branched chainAn alkylene group of (a); radical R3'' is selected from hydrogen and C1-20A linear or branched alkyl group; radicals R in m repeating units4'' the same or different from each other, each independently selected from hydrogen, C1-20A linear or branched alkyl group; radicals R in m repeating units5'' are the same or different from each other and are each independently selected from hydrogen, C1-20A linear or branched alkyl group; m is a positive integer between 1 and 10.
7. The composition according to claim 6, wherein the group R1'' is selected from the group consisting of a single bond and C1-4A linear or branched alkylene group; radical R in m repeating units2'' are each independently selected from the group consisting of a single bond, C1-4A linear or branched alkylene group; radical R3'' is selected from hydrogen, C1-4A linear or branched alkyl group; radicals R in m repeating units4'' are each independently selected from hydrogen, C1-4A linear or branched alkyl group; radical R in m repeating units5'' are each independently selected from hydrogen, C1-4A linear or branched alkyl group; m is a positive integer between 1 and 3.
8. A composition according to claim 6, wherein, in the formula (X), the radicals R1”、R3”、R5"equal to or different from each other, each independently selected from hydrogen, C1-4A linear or branched alkyl group; each radical R2”、R4One group in' is selected from the group represented by the general formula (Y), and the other group is selected from hydrogen.
9. The composition according to claim 6, wherein the phenol compound represented by the general formula (X) is subjected to a sulfurization reaction and then the sulfurized product thereof is subjected to a phosphonoylation reaction; or the phenol compound represented by the general formula (X) is first subjected to a phosphonothioylation reaction, and then the phosphonothioylation product is subjected to a sulfurization reaction.
10. The composition according to claim 9, characterized in that the vulcanization reaction comprises the step of reacting the phenol compound represented by the general formula (X) or the product of the thiophosphoryl acylation of the phenol compound represented by the general formula (X) with a vulcanizing agent.
11. Composition according to claim 10, characterized in that the vulcanizing agent is an inorganic vulcanizing agent and/or an organic vulcanizing agent.
12. Composition according to claim 11, characterized in that the inorganic vulcanizing agent is selected from sulphur, Na2S、K2S、ZnS、H2One or more of S and SCl; the organosulfurizing agent is selected from one or more of di-t-butyl sulfide, dimethyl disulfide, dimethyl sulfide, ethyl mercaptan, n-butyl mercaptan, and t-nonyl polysulfide.
13. The composition according to claim 10, characterized in that the molar ratio of the phenol compound represented by the general formula (X) to the vulcanizing agent is 1: 1-6, wherein the temperature of the vulcanization reaction is 100-240 ℃.
14. The composition according to claim 10, characterized in that the molar ratio of the phenol compound represented by the general formula (X) to the vulcanizing agent is 1: 2-4, wherein the temperature of the vulcanization reaction is 140-190 ℃.
15. A composition according to claim 6, characterised in that the said thiophosphoryl acylating agent has the formula (Z):
Figure FDA0003613543160000061
wherein R is0Selected from H, C6～C20Aryl radical, C1-300A linear or branched alkyl group; the group A is selected from F, Cl, Br, I and OH.
16. Composition according to claim 15, characterized in that R0Selected from phenyl, C1～C14Alkyl benzeneBase, C1～C20A linear or branched alkyl group; the group A is selected from Cl and Br.
17. The composition according to claim 6, wherein the reaction conditions of the sulfurized product of the phenol compound represented by the formula (X) or the phenol compound represented by the formula (X) with a thiophosphoryl acylating agent are: the mol ratio of the sulfur-phosphorus acylating agent to the phenol compound shown by the general formula (X) is 1: 1-10; the reaction temperature is 50-150 ℃.
18. The composition according to claim 6, wherein the reaction conditions of the sulfurized product of a phenol compound represented by the formula (X) or the phenol compound represented by the formula (X) with a thiophosphoryl acylating agent are: the mol ratio of the sulfur-phosphorus acylating agent to the phenol compound shown by the general formula (X) is 1: 1-5; the reaction temperature is 60-100 ℃.
19. The composition according to any one of claims 1 to 18, wherein the antioxidant is an amine antioxidant and/or a phenol antioxidant; the antirust agent is one or more of phosphate amine salt, alkenyl succinate, alkaline barium naphthalene sulfonate and barium petroleum sulfonate; the optional antifoaming agent is methyl silicone oil and/or siloxane; the lubricating base oil is a synthetic lubricating base oil.
20. A method for producing an antirust oil composition as claimed in any one of claims 1 to 19, which comprises the step of mixing the components therein.
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GB8522833D0 (en) * 1985-09-16 1985-10-23 Exxon Chemical Patents Inc Dithiophosphonates
US5387353A (en) * 1993-11-02 1995-02-07 The Dow Chemical Company Lubricity additives for high temperature lubricants
JPH0827170A (en) * 1994-07-13 1996-01-30 Ikari Yakuhin Kk Organophosphorus agent and herbicide, germicide and insecticide containing the same agent as active component

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3256189A (en) * 1962-10-18 1966-06-14 Texaco Inc Hydrocarbyl ether reaction products
GB1070314A (en) * 1964-01-31 1967-06-01 Shell Int Research Improvements in or relating to lubricant compositions
US4051201A (en) * 1970-04-06 1977-09-27 Stauffer Chemical Company Thiobisphenol esters of pentavalent phosphorus acids
GB1309225A (en) * 1970-04-28 1973-03-07 Monsanto Co Refining esters of organophosphorus acids
US4208357A (en) * 1974-09-06 1980-06-17 The Lubrizol Corporation Process for preparing phosphorus and sulfur containing amides and thioamides
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